EP0526602A1 - Rezeptor zur Messung der Quantität eines Bestandteils in Lösung. - Google Patents

Rezeptor zur Messung der Quantität eines Bestandteils in Lösung.

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Publication number
EP0526602A1
EP0526602A1 EP92903775A EP92903775A EP0526602A1 EP 0526602 A1 EP0526602 A1 EP 0526602A1 EP 92903775 A EP92903775 A EP 92903775A EP 92903775 A EP92903775 A EP 92903775A EP 0526602 A1 EP0526602 A1 EP 0526602A1
Authority
EP
European Patent Office
Prior art keywords
sensor according
mediator
sensor
measuring
bipyridine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92903775A
Other languages
English (en)
French (fr)
Other versions
EP0526602B1 (de
Inventor
Michael Graetzel
David Fraser
Shaik Mohammed Zakeeruddin
Jean-Paul Randin
Erik Jan Frenkel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asulab AG
Original Assignee
Asulab AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asulab AG filed Critical Asulab AG
Publication of EP0526602A1 publication Critical patent/EP0526602A1/de
Application granted granted Critical
Publication of EP0526602B1 publication Critical patent/EP0526602B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/001—Enzyme electrodes
    • C12Q1/005—Enzyme electrodes involving specific analytes or enzymes
    • C12Q1/006—Enzyme electrodes involving specific analytes or enzymes for glucose
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/001—Enzyme electrodes
    • C12Q1/004—Enzyme electrodes mediator-assisted
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S435/00—Chemistry: molecular biology and microbiology
    • Y10S435/817—Enzyme or microbe electrode

Definitions

  • the present invention relates to a sensor for measuring the
  • insulin pumps in diabetics.
  • These insulin pumps must be fitted with glucose measurement devices which can also be planted and which, depending on the blood glucose level measured, give information to the pump for the possible start-up of the latter.
  • glucose oxidase GOD
  • GOD is a flavoprotein, (obtained for example from molds) which catalyzes the oxidation of glucose, here for example blood glucose, into gluconolactone, with formation of hydrogen peroxide FLO »from molecular oxygen O present in the test solution, here in the blood.
  • This enzyme (GOD) and oxygen have therefore been frequently used in glucose measuring devices in which glucose oxidation was detected by an electrical or optical transducer.
  • a measuring device provided with at least two electrical contacts connected to an ammeter and to display means and on the other hand, a possibly disposable sensor, which can be connected to these two electrical contacts.
  • This sensor comprises at least two electrodes, one for reference and the other for measurement.
  • the measurement electrode comprises a metallic conductor covered with an enzyme specific to the product that Ton seeks to detect.
  • Figure 2 attached illustrates the chemical reactions occurring at this measuring electrode.
  • the product to be tested here glucose
  • the enzyme here oxidized GOD
  • Toxygen 0 2 which passes to the reduced state H ** > and which then transfers two electrons e " to the electrical conductor C whose potential is fixed and is around 650 mV.
  • Oxygen therefore has a mediating role, since it allows the transfer of electrons.
  • This transfer of electrons proportional to the quantity of glucose present in the solution to be tested is then measured by the ammeter and the quantity of glucose present in the solution is displayed by the display means of the measuring device.
  • the mediators currently in existence rarely have the ideal properties required, namely, an electrochemical potential adapted to the chosen enzyme, adequate solubility, good chemical stability to light, temperature and pH and rapid interaction with the chosen enzyme.
  • the oxygen optionally present in the solutions to be tested enters into competition with certain mediators according to the diagram of FIG. 3 appended.
  • the mediator Med present on the conductor C continues to react with certain molecules of reduced GOD
  • a certain quantity of the oxygen O 2 possibly present also reacts with other molecules of GOD reduced in forming H 2 0 2 , as seen previously in FIG. 2.
  • the H 2 0 2 traps the electrons coming from the reaction between the GOD and Toxygene and these electrons no longer pass to Telectrode.
  • the amount of oxygen in solution can vary, the amount of trapped electrons also varies. Consequently, there is then no longer any proportionality between the quantity of electrons passing towards Telectrode and the quantity of glucose being in the solution to be tested. Under these conditions, these sensors therefore do not give reliable results.
  • the object of the invention is to remedy the drawbacks mentioned above.
  • the invention relates to a sensor for measuring the quantity of a component in solution, comprising: at least one measuring electrode and one reference electrode, electrically isolated from each other and intended to come into contact with said solution, said electrodes respectively comprising electrical contacts adapted to be connected to a device for processing the signal supplied by said sensor, Measuring telectrode comprising at least one current collector, electrically connected to one of said electrical contacts and covered with a mixture comprising at least one specific redox enzyme of said component and at least one mediator transferring electrons between said enzyme and said current collector.
  • the mediator is chosen from the complexes of a transition metal with at least one bipyridine, terpyridine or phenanthroline ligand, substituted by at least one electron donor group.
  • FIG. 1 illustrates the degradation of glucose in the presence of glucose oxidase GOD
  • FIGS. 2 and 3 are diagrams illustrating the various chemical reactions occurring at the level of the sensors
  • FIG. 4 is a top view of a measuring device provided with 'a sensor according to the invention
  • Figure 5 shows the cyclic voltammetry curves of the tris (4,4' - dimethoxy - 2,2 '- bipyridine) osmium complex in the absence of GOD and glucose, at different scanning speeds
  • FIG. 6 represents substantially the same curves as FIG.
  • FIG. 7 represents three curves illustrating the variation of the current density obtained after 30 seconds (D 3Q ) as a function of the glucose concentration in a physiological solution, for measurements carried out with three types of sensors according to the invention, in which the quantity of carbon powder varies
  • FIG. 8 represents the slope and the ordinate at the orig ine of the curves of FIG. 7, as a function of the quantity of carbon powder
  • FIG. 9 represents three curves illustrating the variation of the current density obtained after 30 seconds (D 30 ) as a function of the concentration of glucose in a solution physiological, for measurements made with three types of sensors according to the invention, in which the amount of glucose oxidase varies
  • FIG. 7 represents three curves illustrating the variation of the current density obtained after 30 seconds (D 3Q ) as a function of the glucose concentration in a physiological solution, for measurements carried out with three types of sensors according to the invention, in which the quantity of carbon powder varies
  • FIG. 8 represents the slope and the ordinate at the orig ine of the curves of FIG.
  • FIG. 10 represents the slope and the ordinate at the origin of the curves of FIG. 9, as a function of the amount of glucose oxidase
  • FIG. 11 represents three curves illustrating the variation in the current density obtained after 30 seconds (D, Q) as a function of the glucose concentration in a physiological solution, for measurements carried out with three types of sensors according to the invention, in which the quantity of mediator varies
  • FIG. 12 represents the slope and the ordinate at the origin of the curves of FIG. 11, as a function of the quantity of mediator
  • FIG. 13 represents measurements of the current density obtained as a function of the glucose concentration, these measurements being carried out in the blood and in a phosphate buffer with glucose sensors provided respectively with one of the two preferred mediators according to the invention
  • FIGS. 15 and 16 represent measurements of the current density obtained as a function of the glucose concentration, these measurements being carried out with sensors according to the invention in samples of physiological solution having respectively various concentrations of acetaminophenol and ascorbic acid.
  • the device 2 for measuring the quantity of a given component in a solution comprises a sensor 6 according to the invention and a device 4 for processing the signal supplied by said sensor.
  • This device 4 is known per se and has the general shape of a pen. It is obvious that this form is not limitative of the invention.
  • This pen 4 comprises at one of its ends, referenced 8, a cavity 10 in which are housed two first electrical contacts 12, 14 electrically connected to an ammeter (not shown).
  • This ammeter is itself connected to a display 16 indicating the concentration of the component sought in a given solution. This concentration is displayed, for example in mg / dl or in mmol / 1.
  • the pen 4 further comprises a plug 18 which covers its ex ⁇ end 8 and protect the contacts 12, 14, when the said pen is not in use.
  • the sensor 6 according to the invention has for example the shape of a rectangular insulating strip that can be introduced by one of its ends referenced 19 in the cavity 10 of the pen 4. It will be noted that this sensor 6 is for single use.
  • the reference electrode 22 comprises a strip 24 made of electrically conductive material.
  • This strip 24 has three zones, a so-called electrical contact zone 26, provided towards the end 19 of said sensor, a central zone 28 called “conductive track” and a zone 30, provided at the other end of the sensor and called “current collector” .
  • the measuring electrode 20 comprises a strip 32 made of electrically conductive material.
  • This strip 32 also includes three zones, an electrical contact 34, a conductive track 36 and a current collector 37, unlike collector 30, covered with a mixture 38.
  • the mixture 38 comprises at least one redox enzyme specific for the component to be measured and at least one mediator transferring the electrons between said enzyme and the current collector formed in band 32.
  • the aforementioned mixture 38 can also comprise at least one active conductive material and / or at least one additive which will be described later.
  • the mediator transfers the electrons between the enzyme and this active conductive material which in turn transfers the electrons to the current collector.
  • the drop 40 of the sample of solution to be tested is deposited astride the two electrodes 20 and 22 as illustrated in FIG. 4.
  • the electrical circuit constituted by the ammeter, the contacts 14 and 26, the conductive track 28 , the collector 30, the drop of solution 40, the mixture 38, the collector 37, the conductive track 36 and the contacts 34 and 12, is closed.
  • the measuring device 2 which has just been described is intended for carrying out in vitro measurements, however it is quite obvious that the sensor 6 could be used in vivo, in implantable measuring devices. In this case, its shape or dimensions would be adapted to this new application. Furthermore, to obtain increased precision, a second measurement electrode could be added, identical to the measurement electrode 20 but without Tenzyme or with denatured Tenzyme.
  • the drop 40 of solution to be tested can be of a biological nature, for example, blood or blood from a human or an animal, or a fermentation medium for microorganisms. It may possibly be of synthetic origin, for example a synthetic buffer containing elements to be analyzed.
  • glucose oxidase GOD is used, for example a GOD having an activity of approximately 250 IU, obtained from a mold of Aspergillus niger.
  • the active conductive material optionally used is preferably in the form of a powder of carbon, graphite, gold, platinum, palladium or oxide of conductive metal, for example oxide of ruthenium or in the form of a conductive polymer film, for example polypyrrole.
  • a carbon powder Preferably use a carbon powder.
  • an additive forming a network for immobilizing the enzyme, the mediator and / or the active conductive material on the surface of the collector 37 of the measuring telectrode 20.
  • This additive is for example the bovine serum albumin (BSA), glutaraldehyde, carbodiimide or water soluble polymers.
  • the strips of electrically conductive material 24, 32 are produced for example, in the form of a layer of a material chosen from Tor, silver, platinum, palladium, carbon, graphite or a conductive metal oxide, such as a ruthé ⁇ nium oxide, for example.
  • the strip 24 corresponding to the reference telectrode 22 is made of silver and the strip 32 corresponding to the measurement telectrode 20 is made of platinum. More specifically, the part of the strip 24 corresponding to the current collector 30 is partially chlorinated. It has been discovered that a new family of transition metal complexes with at least one bipyridine, terpyridine or phenanthroline ligand substituted by at least one electron donor group has good mediator properties.
  • the electron donor group is an OH group, an alkoxy group, an aryloxy group or a primary, secondary or tertiary amino group.
  • the tris complex (4.4 '- dimethoxy - 2.2' - bipyridine) is preferably chosen from the abovementioned mediators. osmium or the bis (4,4 '- dimethoxy - 2,2' - bipyridine) mono (4,4 '- dimethyl - 2,2' - bipyridine) osmium complex.
  • the mixture 38 deposited on the collector of the measuring electrode 20 comprises for 1 ml of 10 mM phosphate buffer adjusted to pH 6.8: 1 to 1000 g of carbon powder, preferably 1 at 100 mg or better approximately 10 mg; 1 to 2000 IU of glucose oxidase per mg of carbon powder, preferably 10 to 300
  • the mixture 38 comprises 1 to 2000 IU of glucose oxidase per mg of carbon powder, preferably 10 to 3000 IU or better 100 IU and 1 to 10000 ⁇ mol of mediator per mg of carbon powder, preferably 10 to 300 ⁇ mol or better 50 ⁇ mol.
  • the sensor according to the invention provided with the aforementioned mediators, has a certain number of properties varying according to the ligands used and the substitutions made on these ligands.
  • the aforementioned complex was tested by cyclic voltammetry in direct current, in order to determine on the one hand its normal redox potential E ° and on the other hand the speed constant k.
  • This constant k corresponds to the electron transfer reaction, from GOD, to the mediator.
  • the cyclic voltammetry consists in having in the solution to be analyzed, a working electrode, a counter electrode and a reference electrode, then in carrying out a scanning, at constant speed and between two terminals, of the potential of working electrode and in measuring the intensity of the current obtained.
  • the curves of Figures 5 and 6 represent the results obtained by this method.
  • the mediator performs an electrochemically reversible transfer of an electron to the current collectors described above.
  • Table 1 gives the values of the speed constants k found and the normal redox potentials E ° in mV relative to a calomel reference electrode (SCE).
  • N.D. means undetermined.
  • the family of mediators has a very wide range of redox potentials, varying between - 1000 mV and + 425 mV (relative to a reference electrode with calomel SCE).
  • the lower limit of this range is much lower than all the redox potentials of the mediators described so far in the literature.
  • this range of potentials is also much wider than that obtained with the ferrocene family. This is due to the large number of substituents that can be used and the greater number of possible combinations of substitutions.
  • the second order constant k f corresponding to the rate constant of the redox reaction between Tenzyme and the mediator according to the invention is much faster than with the other mediators known up to now and is faster than with Toxy ⁇ gene.
  • the oxygen has a constant k of 1.5.10 M “ .s " only. This limits the previously described problems of oxygen competition with the mediator during the reaction of electron transfer from the GOD. Likewise, the other competition reactions which take place much more slowly do not influence the result of the measuring device.
  • the various sensors prepared in this way were used for potentiostatic measurements, at a potential of 300 mV, in multiple blood samples containing varying amounts of glucose. The results are illustrated below.
  • the PBS phosphate buffer used here and in the experiments mentioned below is a 10 mM buffer adjusted to pH 6.8.
  • the physiological solution is composed of 115 mM NaCl, 25 mM KC1, K 2 HP0 4 . 3H 2 05 M and H £ P0 4 0.5 mM.
  • curve C is substantially horizontal between 17 and 83 mg of carbon, which means that between these two values, the amount of carbon has little influence on the results of the sensor. However, since a thin layer of carbon has better mechanical and diffusional properties, it is preferred to use as little carbon as possible. In addition, it can be seen that the value of the ordinate at the origin of the line a (8 mg of carbon per ml) is the lowest, which means that Ton has the lowest residual current.
  • the lines a, b, c of FIG. 9 correspond respectively to the results observed with sensors containing 87, 175 and 350 IU of glucose oxidase per mg of carbon powder.
  • the curves C. and C 2 in FIG. 10 respectively represent the slope (m) and the ordinate at the origin.
  • the abscissa axis of Figure 10 expresses the amount of GOD in IU per mg of carbon powder.
  • curve C is substantially horizontal, which means that between these two values the amount of GOD has little influence on the results.
  • the intercept of the line a is the lowest which means that we have the lowest residual current.
  • the lines a, b, c of FIG. 11 correspond respectively to the results observed with 33; 67 and 133 ⁇ mol of this complex per mg of carbon.
  • the curves C and C 2 in FIG. 12 represent the slope (m) and the ordinate respectively at the origin.
  • the abscissa axis of FIG. 12 represents the quantity of mediator in ⁇ mol per mg of carbon powder.
  • the curves in FIG. 13 illustrate potentiostatic measurements carried out with sensors presenting as mediator the two preferred complexes of the invention and by varying the concentration of glucose in samples of blood or of PBS phosphate buffer. The measurements were made at 300 V and the current density D20 was read after 20 seconds.
  • Curves C. and C- correspond respectively to measurements made in phosphate buffer and in blood with a sensor using the tris (4,4 '- dimethoxy - 2,2'- bipyridine) osmium complex
  • curves C 2 and C respectively correspond to measurements carried out in the phosphate buffer and in the blood with a sensor using the bis (4,4 '- dimethoxy - 2,2' - bipyridine) mono complex (4,4 ' - dimethyl - 2,2 '- bipyridine) of osmium.
  • the different curves have a linear plot and a sufficiently large slope up to values of 20 mM of glucose. Consequently, in a patient where the physiological glucose values can typically vary from 3 to 20 M, the sensor according to the invention can be reliably used, since a small variation in the glucose concentration corresponds a sufficient variation in the density of measured current.
  • the curves in FIG. 14 illustrate the variations in the current density (D30) obtained after 30 seconds, as a function of the glucose concentration in artificially reconstituted human blood.
  • the blood samples were prepared as follows. Plasma and blood cells were separated by centrifugation at 3000 rpm for 15 minutes at 4 ° C. Next, the blood was reconstituted to obtain various hematocrit values (0.35; 0.50 and 0.60) and certain amounts of glucose were added to these samples.
  • the glucose concentration was measured using a calibrated laboratory device, for example the device referenced 23A, (available from Yellow Springs Instrument, Yellow Springs, 0HI0).
  • the potentiostatic measurements were carried out at 300 V with sensors presenting as mediator the bis (4,4 '- dimethoxy - 2,2' - biypridine) mono (4,4 '- dimethyl - 2,2' - bipyridine) complex. osmium The current density measurements were made after 30 seconds.
  • Curves C ,, C 2 and C-. correspond respectively to samples containing 35% of cells and 65% of plasma, 50% of cells and 50% of plasma and 60% of cells and 40% of plasma.
  • Curve C 2 corresponds to a normal hematocrit. It can be seen that the curve C-, (hematocrit 0.60) corresponding to a high hematocrit, practically does not differ from the curve C 2 .
  • curve C (hematocrit 0.35) corresponding to141tocrit of an anemic person differs from curve C 2 ⁇
  • the senor according to the invention gives reliable results in a patient with a high hematocrit but less reliable in a person with anemia.
  • the potentiostatic measurements were made at 300 mV.
  • the current density (D o n) was read after 30 seconds.
  • the different curves represent the variations of the current density as a function of glucose concentration, when different amounts of each of the drugs tested are present in a sample of physiological solution.
  • Figure 15 illustrates the curves obtained.
  • Curves C., C 2 (dotted lines) and C 3 correspond respectively to concentrations of 0, 50 and 500 ⁇ M of acetaminophenol.
  • the value of 50 ⁇ M corresponds to what is found in a patient who has taken acetaminophenol in a normal dosage, on the other hand the value of 500 ⁇ M corresponds to an excess. It can be seen that between 4 and 10 mM of glucose (which corresponds substantially to physiological values), the presence of this medicament has little influence on the results provided by this sensor, since all the curves are substantially superimposed.
  • Figure 16 illustrates the curves obtained. Curves C ,, C 2 and C 3 correspond respectively to concentrations of 0, 100 and 1000 ⁇ M of ascorbic acid per ml of blood.
  • the value of 100 ⁇ M corresponds to the values found in a patient having absorbed vitamin C according to a normal dosage
  • the value of 1000 ⁇ M (curve C 3 ) corresponds to an excess of ascorbic acid .

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  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
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  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
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EP92903775A 1991-02-21 1992-02-19 Rezeptor zur Messung der Quantität eines Bestandteils in Lösung Expired - Lifetime EP0526602B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9102200 1991-02-21
FR919102200A FR2673289B1 (fr) 1991-02-21 1991-02-21 Capteur de mesure de la quantite d'un composant en solution.
PCT/CH1992/000034 WO1992014836A1 (fr) 1991-02-21 1992-02-19 Capteur de mesure de la quantite d'un composant en solution

Publications (2)

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EP0526602A1 true EP0526602A1 (de) 1993-02-10
EP0526602B1 EP0526602B1 (de) 1997-01-02

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US (1) US5378628A (de)
EP (1) EP0526602B1 (de)
JP (1) JP2770250B2 (de)
AT (1) ATE147107T1 (de)
AU (1) AU656360B2 (de)
BG (1) BG96988A (de)
CA (1) CA2080840C (de)
DE (1) DE69216319T2 (de)
FI (1) FI924726A (de)
FR (1) FR2673289B1 (de)
HU (1) HU212451B (de)
PL (1) PL169972B1 (de)
SK (1) SK316592A3 (de)
WO (1) WO1992014836A1 (de)

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FR2673289B1 (fr) 1994-06-17
AU656360B2 (en) 1995-02-02
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CA2080840C (en) 1999-04-06
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US5378628A (en) 1995-01-03
PL169972B1 (pl) 1996-09-30
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